Method of making apertured metal sheets

ABSTRACT

586,003. Etching. KODAK, Ltd., and GRESHAM, D. C. March 25, 1944, No. 5569. [Class 100 (ii)] [Also in Groups XX and XXXVI] Apertured diaphragms comprising a preferably metal foil on a sheet metal base are made by forming stencils on both sides of the base where the holes are required, depositing the foil on the parts not covered by the stencils, removing the latter, and electrolytically or chemically etching the base until the desired holes are formed. The foil may be of nickel and the base of copper. Chemical etching can be effected by ferric chloride solution or dilute nitric acid. The stencil is preferably applied photographically using gum bichromate or silver salt emulsion, or the process of Specification 573,798, [Group XX], the apertures in the positives on both sides of the base being in register and that on the reverse side is made larger. Fig. 4D shows a configuration of slotted graticule forming one of several produced simultaneously on a single sheet by the following method. Slot 26 is drawn as a thick black line on a white lacquered metal background 25 on which the perimeter 27 is also represented as a black line, a reduced positive is made, and from it two negative contact prints are obtained, one, the wide-slot negative, having its slot extended by Indian ink and its perimeter 27 &#34; perforated &#34; with white ink, and then both negatives are photographed to give two accurate final-size positives. One positive is reversed to give a mirror-image, and a sheet of several images of both positives is obtained by a step-and-repeat camera, positive. glass transparencies being made therefrom. The sheets containing the two sets of positives are then registered and the rim 17, 171 of the narrowslot one 12 is detached and glued in place on the wide slot one 13 so as to form a frame, Fig. 5C, in which the chemically-cleaned copper base 16 is inserted between the two positives, the copper plate being previously given on both faces, a layer of resin covered by a sensitized layer, particulars of which are given. Both faces are then exposed to light, the sensitized layer and resin are treated with water and lactic acid to-remove all but the resin stencils, and the plate anodically cleaned, particulars of these processes also being given. A nickel foil layer is then electrolytically deposited, the resin stencil is removed, and copper base etched anodically to make the apertures. Particulars of these processes also are given. The perforations between the graticules enable their easy removal from the sheet individually. The formation of the negatives on the copper is effected in a vacuum frame, Fig. 5B, comprising frames 18, 18&lt;1&gt; hinged together, frame 181 carrying a rubber bead 21 stuck to a rubber apron 22 on which a celluloseacetate sheet 23 is stuck, this sheet together with a glass sheet 20 on frame 18 constituting a sealed enclosure which can be exhausted by means of a tube 24. Specification 585,035, [Group XX], also is referred to.

May 10, 1949. D. c. GRESHAM 2,469,689

METHOD OF MAKING APERTURED METAL SHEETS Filed March 25, 1945 2 Sheets-Sheet 1 Fl 63A.

' *D FIG. 3 B.

-D FI-c.ac. FIGS 0.

l4 Jul? 4 5, \j 7 DONALD C. GRESHAM F 6. /C INVENTOR H WW May 10, 1949. D. c. GRESHAM 9 METHOD OF MAKING APERTURED METAL SHEETS Filed March 25, 1945 2 Sheets-Sheet 2 FIG 6 B.

. FO5/77VE BUS-BAR N/CKE xmopss EGAT/VE BUS BAR ODIES Pas/Tl {Bl/S'BAR N/CKEL AN 2/-/ I {IIIIIIIIIIIIJ WIIIIIII/IIIIII 4 F/GZE I DONALD C.GRE5HAM F, G c INVENTOR 4 I :1 ITORNEYS Patented May 10, 1949 METHOD OF MAKING APER-TURED METAL SHEETS Donald C. Gresham, Wealdstone, England, as-

slgnor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application March 23, 1945, Serial No. 584,453 In Great Britain March 25, 1944 2 Claims.

The invention relates to the making of articles shaped by etching.

For some purposes it is necessary to be able to make articles having holes (which term means any shape of hole, such CS slots) with extremely thin and sharp edges in a relatively thick article. The present invention is directed to a method of making such articles in a relatively simple and repeatable manner. The invention gives an improved ease of producing holes accurately to a predetermined size with sharp outlines and without distorting the shape particularly where the outline has sharp angles which would by most known methods commonly used become rounded.

As a part of some highly precise instruments there is often required a metal foil or foils having highly precise holes or slots. An illustration is a pair of rotating diaphragms as used in some optical work. The invention can also be employed to make invert half-tone printing forms for printing in intaglio. Not only must the holes or slots have an unusually high degree of pre- .vision but at the same time the foil must be ro- "bust. For instance, if holes are made by some known manner in metal foil of say two-thousandths of an inch thick, the sharpness of the edges of the holes is determined by this thickness and therefore while being fairly sharp, the foil itself is too flimsy. If the foil is made thicker, say one-hundredth of an inch, then the kind of .hole usually obtained, for instance by etching from both sides, has rounded edges.

To combine sharpness of edge and robustness is a difiicult problem. Although it is possible to achieve the result by first forming a metal foil, with the desired holes (for instance, by the method described in Loening U. S. application Serial No. 580,290, and then after placing it on a temporary backing, forming a resist, and plating the remainder with a metal deposit, and repeating this say twice more using resists and making further metal depositions, and finally removing the temporary backing and the resists, the result is not entirely satisfactory apart from the tedious and troublesome nature of the whole process.

We have now solved this problem of combining sharpness of edge and robustness in what we believe is a novel manner and gives results not Figs. 3A to 313 are views partly in plan showing apertures etched by my method;

Fig. 4A is a perspective View of a vacuum frame used in my invention, Fig. 4B is a view in section of the vacuum frame and Fig. 4C is a sectional view of an assembly with my etched plate;

Fig. 5 is a view partly in section of an exposing box used in my invention;

Fig. 6A is a sectional View of a plating bath and Fig. 6B is a plan view of the plating apparatus.

In the present invention we start with an imperforate sheet which will ultimately form a permanent strengthening plate and we form the foil on it by deposition and then etch away the strengthening plate opposite the holes in the foil.

For instance, in performing the invention we can use two different substances of such nature that when both together are made the anode in an electrolytic bath and a current is passed from such anode to a cathode, the one substance is preferentially removed electrolytically from the anode. Two such substances are nickel and copper; if the nickel foil with the holes is first formed by deposition of nickel on a copper strengthening plate and then together they are made the anode in a so-called copper plating bath then the copper is etched while the nickel is not etched (or hardly at all).

In using two such substances according to the invention, a thin design indicated as 9 in Fig. 1 can be formed by deposition of the less etchable substance (which is preferably a metal) on the Figs. 2A to 2E are sectional views of a two- I layer plate;

ing can be used but is surface of the mort etchable substance forming the strengthening base It] by first forming a negative photographic resist on the strengthening base and then depositing the less etchable substance in places unprotected by the resist, so as to form the foil, whereafter the whole (for instance a design in nickel foil on a copper strengthening base) is then made the anode in an electrolytic bath, and current is passed to etch away the strengthening base opposite the holes in the foil to give the result shown in Fig. 13. However, if

' this etching is not continued until the strengthening base is perforated, the result will be as shown in Fig. 1C; this illustrates the kind of cavity which is useful in the production of invert half-tone printing forms for printing by intaglio. Instead of etching electrolytically, chemical etchusually not so good; thus in the case of a nickel foil design on a copper plate, etching can be done by simply applying a solution of ferric chloride or dilute nitric acid.

partly in section and The invention is especially valuable when in order to obtain the maximum robustness two metal foil designs are formed in register on both sides of the strengthening base which gives a re sult greatly superior to that obtained when the metal foil design is formed on the one side only.

In a preferred method of performing the in vention the said design is formed photographically, for example, by first coatingon-bot-h sides of the strengthening base light sensitive layers of bichromated glue in known manner, exposing. the latter in register to an image or images'and' forming resists therein in known manner, forming the foil thereon by deposition on the unprotected areas on both sides of the said base, then removingthe resists and'subsequently making the whole the'anode in anelectrolytic bath and passing current therethrough until the basebut not the foil is so'removedthat holes are formed right through the base which areofa greater width than the holes in the foil.

The photographic resists can be formed in other ways, for instance by coating light sensitive silver salt emulsion (e. g. a gelatino-silver halide emulsion) layers instead of gum bichromate or by the process described in U. S. application Serial No. 566,027, now Patent 2,459,129, granted January 11, 1949;: or finished photographic images or finished resists can be transferred-from other supports.

The invention is illustrated by the following exampl which illustratesthe production of slots in metal sheets. course, purely diagrammatic. as-follows-z (1) Two photographic positivesare made ofa desired graticule, one having clear lines (on an opaque background) of exactly the width of the requiredslots as shown in planin Fig, 3A,- and the second (not shown) having similar clear lines but about 2 or 3'times as wide. I

(2-) A sheet I I of copper of 0.012- inch thick shown in section in Fig. 2A- is coated on both sides with bichromated glue 2: and 2.

(3) One side is then exposed to t-he-firstpositive and the other side to the second positive, the lines of: the first positive registering withthe centres of thelines-of' the second positive.-

(4-)- Then resists are' formed in known manner in the'twoglue'layer-s. Theresists'are preferably burnt-in as in the standardi practice of half-tone block making. The sheet H is now shown in Fig.- 23 hearing the resists 3 and 3',

(5) After suitable chemical cleaning, the un- The procedure is protected copperonbothsidesofthesheet is electro-nickel plated to'forma foil of a thickness of only about one-half ofone thousandthof aninch as shown in'Figur-e 2C.

(6) The resists are then removedby boiling the sheet in caustic soda solution. The sheet is now shown in Fig. 213 where 4 and 4' show the nickel plating;

(7 The composite sheet is then made the anode in a copper electro-plating bath and the copper alone isetched out from both sides simultaneously until there are not only slots formed right through the copper but the copper has-also been-removed to a greater width (at least in the center of the thickness of the sheet) than the width of the. slots in the nickel. This result is shown in section in Fig. 2E.

By forming the design by depositing the nickel in the spaces of a photographically formed resist, extremely sharp and clean edges to the nickel deposit can be formed. While Fig. 2E shows in Allthe drawings herein are, of

The following description illustrates in greater detail the making of a number of graticules of the kind'shown in Fig. 3A, each consisting of a very small metal sheet 25 containing very narrow slots 26 of the shape illustrated in Figs. 2E and 3A. The stepsin making these graticules are as follows:

Part'I.Prepara'tion of printing negatives (19 A negative'drawing of the desired graticule is prepared 40 times final size on white lacquered metal. This drawing consists of a whitebac'kground 25 (representing the metal of the desired graticule) on which is drawn the slot 26 as a thick black line and the'perimeter 21 alsoas a black line.

(2) The metal sheet hearing such drawing: is set up on a largecamera' asused for photo-template work and apositive is made on a silver halide emulsion at Ag-reduction, thus giving a reproduction of ten timesfinal'size.

(3 From such positive two negative contact prints-are made.

(4) One-of these negativep'rints is now modified by drawing over it with India ink, adding 0.1 to-all sides of: each slot and making some small breaks in the perimeter line by painting over it with white ink. This altered print will be the original for the back image and the small breaks will provide tie-bars to hold the etched graticules intothe sheet at the final stage;

(59 The negative prints are now set up on a precision camera; as normally used for making graticule' negativesand reduced very accurately to' 'final size to givepositiv-e'images- (6') From the so formed" positive with the wide slot, a contact print is made andprocessed' by reversaltogiv-e a mirror-image positive;

('7')- From each of these positivesfrom step (3) and step (6) astep-and-repeatnegativeis made on a, step-and repeat camera. It has been found that a stepped-up'negativebearing eight images-in one direction" and six 'i'n the other'isa convenient size.

(8) The st'epped-u'pnegativeis used'as a masterfrom which positi ve transparencies are made by contact.

(9)- Theedges'of the wide line positive transparencies are now out o1? close to the images-and the oifcuts are'kept carefully. The pairs of positives are registered face to face, so that the slots on the fine-slotpositive are in the centre of the slotson-the wide-slot positive, and fastened together with bulldog clips.

(10) The-edgeswhich'were cut from the wideslot positive are now matched up again and stuck firmly tothe fine-slot positive with: glue while the cut-down positive isstillclipped in position. When the glue isdry the bulldog clips are removed and the cut-down positive can be dropped out of the glass frame formed on the larger one. This ensures that whenever the cut-down positive is dropped into the frame the images on the two positives will come into register (see step 18 below).

Part II .Preparation of graticules from negatives (11) A sheet of polished ,photogravure copper 0.012" thick is out very slightly smaller than the cut-down positive. Great care is taken to ensure that no burr is left on the edges and that there are no turned-up corners.

(12) The copper is cleaned by dipping into a tank of the following solution for 5 seconds:

Concentrated hydrochloric acid cc- '75 Concentrated nitric acid cc 25 'The plate is drained; rinsed in a 0.05% solution of wetting agent and dried on a whirler which has been fitted so that the plate can be supported by the corners without the underside coming into contact with anything.

(13) The plate, while still on the whirler, is

idusted carefully and a liberal quantity of the following solution is poured on and spread to the edge with aglass rod:

Phenol-formaldehyde resin gm 80 Ethyl acetate cc 200 Oil soluble yellow (color index No. 24) gm 4 Waxoline red (color index No. 253) gm 4 The whirler is then started and run at 800 minutes and then removed and. cooled to room temperature.

(16) The plate is replaced on the whirler and coated at 800 R. P. M. with a solution made as follows:

Disperse 75 gm. of gum acacia in 300 cc. of

distilled water containing 0.25% of chloroform. To 90 cc. of this dispersion add cc. of 20% ammonium dichromate solution.

(1'7) The plate is turned over and the other side is coated in the same way.

(18) The copper sheet, sensitised on both sides, is now placed within the glass edging on the fineslot positive and the wide-slot positive is dropped in on top of it. This assembly is shown in section in Fig. 4c. The fine-slot positive is shown as H! and the wide-slot positive as l3, their glass supports being It and I5 respectively. The copper plate between them is shown as It. The said off-cuts mentioned in step (10) are shown as I! and II.

This assembly is then put in a special vacuum pressure frame which has been developed for this process.

This vacuum frame is shown in perspective in Fig. 4A and in section in Fig. 4B where l8 and and cellulose acetate window 23 is quite air tight y and can be evacuated by suction through the tube 24. The assembly shown in Fig. 4C is placed between the sheets 20 and 23 and then the frame is evacuated.

(19) Both sides of the vacuum frame may be successively exposed for 6 minutes at 18" from ill 2120A open arc lamp, care beingtaken that the vacuum in the frame is maintained while the frame is turned over but we prefer to use the special exposing box shown in Fig. 5 having a high intensity, mercury vapor lamp L and L at each end and the double-sided vacuum frame I8 and I53 between them. This will allow both exposures to be made simultaneously.

(20) The copper plate is removed from between the positives and all the gum coating on both sides which has not been light-hardened is washed out by spraying both sides of the plate With'cold water, and finally rinsing it in a dish of Water at 80-85 F., leaving on the copper surfaces a coating of Bakelite, on which are hardened gum areas where the slots are to be formed ultimately.

(21) The copper plate is dried on the whirler and then slightly warmed in a warm air current.

(22) The copper plate is laid fine-slot image side upwards on a sheet of clean, warmed blotting paper and developed with lactic acid containing 10% of ethyl lactate which is gently swabbed over the plate with a pledget of cotton-wool. This is continued until all the phenolformaldehyde layer which is unprotected by the gum stencil has been dissolved.

(23) The action of the developing solution is then immediately stopped by swabbing over with 50% lactic acid and water. This also has the effect of removing the hardened gum stencil.

(24) The plate is turned over, placed on a clean sheet of blotting paper and the development process is carried out on the back exactly as described for the front.

(25) Both sides are now vigorously swabbed with 50% lactic acid to make sure that every trace of hardened gum is removed, leaving on each side a negative image of phenolformaldehyde resin only. The plate is then washed thoroughly and whirled dry.

(26) The plate is suspended by its edge for minutes in an oven at 140 C., removed and cooled to room temperature.

(27) The plate is then connected as the anode in an electrolytic cleaning bath. The bath con sists of:

Potassium cyanide gm Sodium carbonate, anhy gm 100 Water to cc 1000 The cathode is of rolled copper and a current is passed for 5 seconds with a potential difference across the electrodes of 6 volts.

(28) The plate is rinsed in water and dipped in 10% sulphuric acid.

(29) Without draining the plate is put into the nickel plating bath as the cathode, as shown in Fig. 6A and 6B, and arrangements are made for the potential difference between the electrodes to be 2.25 volts. The plating bath is made from a standard nickel plating mixture. The anodes are standard nickel ones arranged on both sides of the plate and the bath is adjusted daily, to a pH of 5.6 with dilute sulphuric acid. (The carry-over of acid from the acid-dip is almost sufficient to keep the pH constant and this is the reason for not draining the plate before putting it in the plating bath.) The density of the bath is maintained at 13 'I'waddell and the inter-electrode distance is 10 cm. Care is taken that the current is switched on before the plate is introduced into the bath and the plating is continued for 45 minutes at F.

(30) The nickel plated sheet is removed from 7 the plating bath,- rinsed and boiled in the following solution until all the phenol-formaldehyde resin resist is removed Sodium hydroxide gm 20 Methyl'ated' spirit cc 10 Water to cc 100 The plate is then washed in cold water.

(31) The plate is now made the anode in a bath of 20% copper sulphate With a potential difference of 10 volts between the electrodes until the slots of the graticule have been etched right through as required. This takes about 15 minutes.

('32) The plate, now etched so that the graticul'es are just holding in by thin tie-bars on the back is washed and dried and the individual graticulesare broken out of the sheet.

I claim:

1. The method of making an apertured' sheet of composite copper and nickel layers, which comprises forming in the same zone on both sides of a relatively thick imperfcrate copper sheet, non-conductive colloid stencils covering both sides of said copper sheet where said aperture is required, depositing on the parts of both sides of said copper sheet not protected by said stencils, thin layers of nickel, then removing said stencils and making the copper sheet the anode in a copper plating bath and passing an electric current between said anode and a oathode until the copper at the parts of said copper sheet where the nickel is absent is removed to a greater width than the width of the aperture in the nickel foil.

2. The method according to claim 1 in which said stencil is composed of areas which are larger on one side of said copper sheet than corresponding areas on the opposite side of said sheet.

DONALD C. GRESHAM.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 378,423 Baynes Feb, 28, 1888 2,226,383 Norris Dec. 24, 1940 2,282,203 Norris May 5, 1942 2,332,592 Norris Oct. 26,- 1943 

